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Syntheses, Crystal Structures, and Photocatalytic Properties of a Series of Mercury Thioantimonates Directed by Transition Metal Complexes

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posted on 07.05.2014, 00:00 by Cheng-Yang Yue, Xiao-Wu Lei, Rui-Qiu Liu, Hui-Ping Zhang, Xiu-Rong Zhai, Wen-Peng Li, Meng Zhou, Zhi-Fei Zhao, Yun-Xiang Ma, Ya-Dong Yang
With different transition metal (TM) complexes as structure-directing agents or structure-building units, a series of new mercury thioantimonates with abundant architectures ranging from one-dimensional (1D) ribbons to two-dimensional (2D) layers have been solvothermally synthesized and structurally characterized. Compounds [Co­(en)3]­Hg2Sb2S6 (1) (en = ethylenediamine) and [Ni­(1,2-dap)3]2­HgSb3S7Cl (2, 1,2-dap = 1,2-diaminopropane) contain a discrete 2D [Hg2Sb2S6]n2n layer and 1D [HgSb3S7]n3n chain, respectively. Compounds [Ni­(1,2-dap)3]­HgSb2S5 (3) and [Mn­(dien)2]­HgSb2S5 (4, dien = diethylenetriamine) feature distinct 2D [HgSb2S5]n2n layer and 1D [HgSb2S5]n2n ribbon, respectively, whereas the 1D [HgSb2S5]n2n chains are attached by [TM­(tren)]2+ complexes via TM–S bonds to form 1D {[TM­(tren)]­HgSb2S5}n ribbons in compounds [TM­(tren)]­HgSb2S5 (TM = Mn (5), Fe (6), Co (7), tren = tris­(2-aminoethyl)­amine). Compounds [TM­(dien)2]­Hg3Sb4S10 (TM = Mn (8), Co­(9), Ni­(10)) feature 2D [Hg3Sb4S10]n2n anionic layers separated by [TM­(dien)2]2+ cations. The most interesting structural feature of these compounds is the presence of three different types of coordination environments of Hg centers including linear [HgS2] unit, [HgS3] triangle, and [HgS4] tetrahedron. The optical properties and thermal stabilities of the title compounds were studied by UV–vis spectra and thernogravimetric analyses, respectively. The photocatalytic experiments indicated that 3, 4, and 10 were able to degrade rhodamine B (RhB) under visible irradiation.